Ionic Liquid Stabilized Gelatin–Lignin Films: A Potential UV-Shielding Material with Excellent Mechanical and Antimicrobial Properties

Significant research is currently underway to develop environmentally friendly UV-shielding materials. Herein, we have constructed choline citrate (a biobased ionic liquid, IL) stabilized homogeneous gelatin–lignin UV-shielding films with excellent antimicrobial and mechanical properties. The synthesis procedure of the films is less energy demanding, one pot, and sustainable in nature. Prepared films were characterized by mechanical and thermal analysis using UTM and TGA, respectively. ATR-IR and PXRD was employed to explore the possible formation of H-bonding between biopolymers and the IL and the change in crystallinity in films after addition of IL to the gelatin–lignin matrix. Surface morphology of prepared films has been studied using optical microscope, AFM, and field emission SEM (FE-SEM). Optical properties of prepared films were measured using UV/Vis spectroscopy. Antimicrobial activity of the prepared films was tested against Bacillus subtilis. Prepared biofilms showed a sun-protection factor (SPF) of up to ≈45.0, large elongation ≈200 %, and tensile strength ≈70 MPa, which are as good as those values exhibited by organic polymeric films, indicating a promising renewable-resources-based material for UV light blocking.     

Effects of chemical composition,mild alkaline pretreatment and particle size on mechanical,thermal, and structural properties of binderless lignocellulosic biopolymers prepared by hot-pressing raw microfibrillated Phoenix dactylifera and Cocos nucifera fibers and leaves

We developed value-added, high-strength lignocellulosic biopolymers by exploiting high-lignin biomass waste of palms. Lignocellulosic biopolymers were prepared by hot-pressing microfibrillated raw and alkaline pre-treated date and coconut fibers and leaves powders consisting of (≤53–≤106 μm) particles in the range 140–180 °C. The obtained biopolymers were subjected to three-point bending strength, water resistance, structural morphology (SEM), thermal stability (TGA/DTG), spectroscopy (FTIR), and crystallinity (XRD) analyses. Findings showed that raw fiber-based and alkaline-pretreated biopolymers exhibited bending strength, water resistance, and thermal stability (~200 °C) superior to those of leaf-based biopolymers. Furthermore, lignocellulosic biopolymers prepared from smaller particles showed enhanced bending and thermal properties, compared to those prepared from large particles. By mechanical and thermal properties, the optimum results were observed for biopolymers pre-treated with 1 wt% NaOH, except for coconut leaf-based biopolymers. Results were correlated to chemical composition and particle size of milled lignocellulosic biomass, allowing for efficient lignin condensation.     

Laccase‐Catalyzed Synthesis of Low‐Molecular‐Weight Lignin‐Like Oligomers and their Application as UV‐Blocking Materials

The laccase‐catalyzed oxidative polymerization of monomeric and dimeric lignin model compounds was carried out with oxygen as the oxidant in aqueous medium. The oligomers were characterized by using gel permeation chromatography (GPC) and matrix‐assisted laser desorption ionization time‐of‐flight mass spectroscopy (MALDI‐TOF MS) analysis. Oxidative polymerization led to the formation of oligomeric species with a number‐average molecular weight (M_n) that ranged from 700 to 2300 Da with a low polydispersity index. Spectroscopic analysis provided insight into the possible modes of linkages present in the oligomers, and the oligomerization is likely to proceed through the formation of C?C linkages between phenolic aromatic rings. The oligomers were found to show good UV light absorption characteristics with high molar extinction coefficient (5000–38 000 m ^?1 cm^?1) in the UV spectral region. The oligomers were blended independently with polyvinyl chloride (PVC) by using solution blending to evaluate the compatibility and UV protection ability of the oligomers. The UV/Vis transmittance spectra of the oligomer‐embedded PVC films indicated that these lignin‐like oligomers possessed a notable ability to block UV light. In particular, oligomers obtained from vanillyl alcohol and the dimeric lignin model were found to show good photostability in accelerated UV weathering experiments. The UV‐blocking characteristics and photostability were finally compared with the commercial low‐molecular‐weight UV stabilizer 2,4‐dihydroxybenzophenone.     

Enhanced deconstruction and dissolution of lignocellulosic biomass in ionic liquid at high water content by lithium chloride

Fabricating an aqueous ionic liquid (IL) for deconstruction and dissolution of lignocellulose is attractive because addition of water could reduce the cost and viscosity of the solvent and improve the biomass processing, but the solvating power of the IL is usually depressed in the presence of water. In the present study, an aqueous IL consisting of 1-butyl-3-methylimidazolium chloride (BmimCl), water, and lithium chloride was fabricated for efficient deconstruction and dissolution of lignocellulose (bamboo). The dissolution of cell wall components (cellulose, lignin, and hemicelluloses) in the aqueous IL was investigated. The results indicated that the presence of water significantly reduced the solvating power of BmimCl; For example, 11.5 % water decreased the dissolution of bamboo in BmimCl from ~97 to ~53 %. Dissolution of cellulose and lignin was specifically depressed. However, addition of lithium chloride was able to improve the tolerance of BmimCl to water and enhance the deconstruction and dissolution of biomass in BmimCl with high water content. It was found that approximately 80 % bamboo could be dissolved in solvent consisting of 45 wt% BmimCl and 55 wt% LiCl·2H₂O (25 wt% overall water content in the solvent). In particular, lignin and hemicelluloses were selectively dissolved by 96 and 92 %, respectively. The undissolved residue was predominantly composed of cellulose (~86 %) with a small amount of lignin (<5 %). BmimCl-LiCl-H₂O is a promising and effective solvent system with low cost and viscosity for biomass processing.     

Analytical strategies for chemical characterization of bio‐oil

Bio‐oils, produced by biomass pyrolysis, have become promising candidates for feedstocks of high value‐added chemicals and alternative sources for transportation fuels. Bio‐oil is such a complicated mixture that contains nonpolar hydrocarbons and polar components which cover almost all kinds of organic oxygenated compounds such as carboxylic acids, alcohols, aldehydes, ketones, esters, furfurals, phenolic compounds, sugar‐like material, and lignin‐derived compounds. Comprehensive characterization of bio‐oil and its subfractions could provide insight into the conversion process of biomass processing, as well as its further utilization as transportation fuels or chemical raw materials. This review focuses on advanced analytical strategies on in‐depth characterization of bio‐oil, which is concerned with gas chromatography, high‐resolution mass spectrometry, FTIR spectroscopy and NMR spectroscopy, offering complementary information for previous reviews.     

Effect of Protic Ionic Liquid and Surfactant Structure on Partitioning of Polyoxyethylene Non‐ionic Surfactants

The partitioning constants and Gibbs free energies of transfer of poly(oxyethylene) n‐alkyl ethers between dodecane and the protic ionic liquids (ILs) ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) are determined. EAN and PAN have a sponge‐like nanostructure that consists of interpenetrating charged and apolar domains. This study reveals that the ILs solvate the hydrophobic and hydrophilic parts of the amphiphiles differently. The ethoxy groups are dissolved in the polar region of both ILs by means of hydrogen bonds. The environment is remarkably water‐like and, as in water, the solubility of the ethoxy groups in EAN decreases on warming, which underscores the critical role of the IL hydrogen‐bond network for solubility. In contrast, amphiphile alkyl chains are not preferentially solvated by the charged or uncharged regions of the ILs. Rather, they experience an average IL composition and, as a result, partitioning from dodecane into the IL increases as the cation alkyl chain is lengthened from ethyl to propyl, because the IL apolar volume fraction increases. Together, these results show that surfactant dissolution in ILs is related to structural compatibility between the head or tail group and the IL nanostructure. Thus, these partitioning studies reveal parameters for the effective molecular design of surfactants in ILs.     

基于离子液的超声辅助萃取小蓼叶中的精油及真实溶剂似导体屏蔽模型研究（英文）

Ionic liquids (ILs) based ultrasonic-assisted extract has been applied for the extraction of essential oil from Persicaria minor leaves. The effects of temperature, sonication time, and particle size of the plant material on the yield of essential oil were investigated. Among the different ILs employed, 1-ethyl-3-methylimidazolium acetate was the most effective, providing a 9.55% yield of the essential oil under optimum conditions (70 ℃, 25 min, IL:hexane ratio of 7:10 (v/v), particle size 60-80 mesh). The performance of 1-ethyl-3-methylimidazolium acetate in the extraction was attributed to its low viscosity and ability to disintegrate the structural matrix of the plant material. The ability of 1-ethyl-3-methylimidazolium acetate was also confirmed using the conductor like-screening model for realistic solvents. This research proves that ILs can be used to extract essential oils from lignocellulosic biomass.     

Selective Activation of C=C Bond in Sustainable Phenolic Compounds from Lignin via Photooxidation: Experiment and Density Functional Theory Calculations

Lignocellulosic biomass can be converted to high‐value phenolic compounds, such as food additives, antioxidants, fragrances and fine chemicals. We investigated photochemical and heterogeneous photocatalytic oxidation of two isomeric phenolic compounds from lignin, isoeugenol and eugenol, in several nonprotic solvents, for the first time by experiment and the density functional theory (DFT) calculations. Photooxidation was conducted under ambient conditions using air, near‐UV light and commercial P25 TiO₂ photocatalyst, and the products were determined by TLC, UV–Vis absorption spectroscopy, HPLC‐UV and HPLC‐MS. Photochemical and photocatalytic oxidation of isoeugenol proceeds via the mild oxidative “dimerization” to produce the lignan dehydrodiisoeugenol (DHDIE), while photooxidation of eugenol does not proceed. The DFT calculations suggest a radical stepwise mechanism for the oxidative “dimerization” of isoeugenol to DHDIE as was calculated for the first time.     

Unusual inorganic phase formation in ultraviolet‐curable organic–inorganic hybrid films

Inorganic–organic hybrid materials were prepared with a cycloaliphatic epoxide adduct of linseed oil with tetraethylorthosilicate (TEOS) oligomers via a cationic UV‐curing process. The TEOS oligomers were prepared in the presence of water and ethanol with hydrochloric acid as a catalyst. The TEOS oligomers were characterized with ¹H and ²⁹Si NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. Hybrid films were cured, and the dynamic mechanical and thermal properties of the hybrid films were evaluated as a function of the TEOS oligomer content. The morphology of the hybrid films was examined with atomic force microscopy, transmission electron microscopy, and small‐angle light scattering. The microscopy and dynamic mechanical data indicated that the hybrid films were heterogeneous materials with various inorganic particle sizes dispersed within the organic matrix. In addition, ²⁹Si solid‐state NMR spectroscopy was used to investigate the coupling between the silicate region and organic regions. A schematic model is proposed to address structural features of hybrid materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1607–1623, 2005     

Preparation and antimicrobial properties of LL‐37 peptide immobilized lignin/caprolactone polymer film

The use of biopolymers has gained priority in tissue engineering and biotechnology, both as dressing material and for enhancing treatment efficiency. There is a demand for new biopolymers designed with protease inhibitors and antimicrobials. LL‐37 is an important antimicrobial peptide in human skin and exhibits a broad spectrum of antimicrobial activity against bacteria, fungi, and viral pathogens. Using lignin which is an abundant carbohydrate polymer in nature and a polyacrylic acid, we prepared a lignin/caprolactone biodegradable film by plastifying caprolactone and polyacyrlic acid. Lignin/caprolactone biodegradable film was activated with CDI and then immobilized LL‐37 peptide. The structure was elucidated in terms of its functional groups by attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), and the morphology of the lignin/caprolactone biodegradable film was characterized by scanning electron microscopy (SEM) before and after the immobilization process. The amount of LL‐37 immobilized was determined by ELISA method. It was found that 97% of LL‐37 peptide was successfully immobilized onto the lignin/caprolactone biodegradable film. Antimicrobial activity was determined in the lignin/caprolactone biodegradable film samples by quantitative antimicrobial activity method. According to the results, LL‐37 immobilized lignin/caprolactone biodegradable film samples were effective on test organisms; Gram‐positive Staphylococcus aureus and Gram‐negative Escherichia coli. In bio‐compatibility assays, the ability to support tissue cell integration was detected by using 3 T3 mouse fibroblasts. Samples were examined under transverse microscope, non‐immobilized sample showed a huge cellular death, whereas LL‐37 immobilized lignin/caprolactone biodegradable film had identical cellular growth with the control group. This dual functional lignin/caprolactone biodegradable film with enhanced antibacterial properties and increased tissue cell compatibility may be used to design new materials for various types of biological applications.     

Rapid Extraction and Analysis of Essential Oil from Cinnamomum Cassia Presl.

An improved solvent-free microwave extraction（ISFME） was used for the extraction of essential oil from dried Cinnamomum cassia Presl. Two kinds of solid microwave absorption media[carbonyl iron powder（CIP） and graphite powder（GP）] were used. When ISFME was applied, the heating rate was enhanced and the extraction time was obviously shorter than that consumed in conventional solvent-free microwave extraction（CSFME）. Twenty-eight kinds of compounds in the essential oil were identified, and the total content fractions of the compounds obtained by CIP-ISFME, GP-ISFME, CSFME, and hydrodistillation（HD） were 96.65%, 96.06%, 97.22%, and 96.29%, respectively. The compounds in the essential oil obtained from Cinnamomum cassia Presl. by ISFME, CSFME, and HD were compared and the quantity of the essential oil was almost the same. The ISFME has been proved to be a feasible way to extract essential oil from dried samples, and there are several obvious advantages in ISFME over those of HD and CSFME, for example, shorter extraction time（30 min） and lower energy consumption.     

Protection Group Effects During α,γ‐Diol Lignin Stabilization Promote High‐Selectivity Monomer Production

Protection groups were introduced during biomass pretreatment to stabilize lignin's α,γ‐diol group during its extraction and prevent its condensation. Acetaldehyde and propionaldehyde stabilized the α,γ‐diol without any aromatic ring alkylation, which significantly increased final product selectivity. The subsequent hydrogenolysis catalyzed by Pd/C generated lignin monomers at near‐theoretical yields based on Klason lignin (48 % from birch, 20 % from spruce, 70 % from high‐syringyl transgenic poplar), and with high selectivity to a single 4‐n‐propanolsyringol product (80 %) in the case of the poplar. Unlike direct hydrogenation of native wood, hydrogenolysis of protected lignin with Ni/C also led to high selectivity to this single product (78 %), paving the way to high‐selectivity lignin upgrading with base metal catalysts. The use of extracted lignin facilitated valorization of polysaccharides, leading to high yields of all three major biomass polymers to a single major product.     

Synthesis,characterization, and photoresponsive studies on lignin functionalized with (E)‐2‐(4‐(naphthalen‐1‐yldiazenyl)phenyl)acetic acid

A chromophoric system (E)‐2‐(4‐(naphthalen‐1‐yldiazenyl)phenyl)acetic acid incorporated onto a nature friendly biopolymeric core material, lignin (technical lignin, lignin sulphonic acid M.W. 52,400), and the photo responsive behavior of the product was investigated. The product was characterized by UV–visible, fluorescence, Fourier transform infrared, and nuclear magnetic resonance spectroscopic methods. The results of the studies show that the incorporation of the chromophoric system on to the lignin core enhanced the light absorption and light stabilization properties of the chromophoric system. The trans‐cis photoisomerization and the reverse cis‐trans thermal conversions were also assisted by the lignin core. The remarkable stability on irradiation shows that this is a novel photoresponsive system with excellent light fastening properties which would find application in coating materials, dyes, paints, inks, and many more. Copyright © 2012 John Wiley & Sons, Ltd.     

Renewable epoxidized cardanol‐based acrylate as a reactive diluent for UV‐curable resins

A novel kind of biobased monomer, epoxidized cardanol‐based acrylate (ECA), was successfully synthesized from cardanol via acrylation and epoxidization. The chemical structure was confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. Then, the ECA was employed to produce UV‐curable films and coatings copolymerized with castor oil‐based polyurethane acrylate. Compared to coatings from petroleum‐based diluent hydroxyethyl acrylate‐based castor oil‐based polyurethane acrylate resins, ECA‐based biomaterials exhibited a little inferior dilution ability but overcome the drawback of high volumetric shrinkage with a special lower value. Moreover, ultimate properties of the UV‐cured biomaterials such as thermal, mechanical, coating, swelling, and hydrophobic properties were investigated. The UV‐curing behavior was investigated using real‐time IR, and the overall double bond conversion was more than 90%. This biobased UV‐curable cardanol‐based diluent shows a promise in “green + green” materials technologies.     

Non-polar Solvent Microwave-Assisted Extraction of Volatile Constituents from Dried Zingiber Officinale Rosc.

A new method, non-polar solvent microwave-assisted extraction （NPSMAE）, was applied to the extraction of essential oil from Zingiber officinale Rosc. in closed-vessel system. By adding microwave absorption mediumcarbonyl iron powders （CIP） into extraction system, the essential oil was extracted by the non-polar solvent （ether） which can be heated by CIP. The constituents of essential oil obtained by NPSMAE were comparable with those obtained by hydrodistillation （HD） by GC-MS analysis, which indicates that NPSMAE is a feasible way to extract essential oil from dried plant materials. The NPSMAE took much less extraction time （5 min） than HD （180 min）, and its extraction efficiency was much higher than that of conventional polar solvent microwave-assisted extraction （PSMAE） and mixed solvent microwave-assisted extraction （MSMAE）. It can be a good alternative for the extraction of volatile constituents from dried plant samples.     

Lignin from sugar cane bagasse: extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels through impedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.     

Microwave-hydrothermal synthesis and photocatalytic properties of biomass charcoal/TiO2 nanocomposites

Biomass charcoal-doped titanium dioxide (C/TiO₂) composites were proposed by microwave-hydrothermal and calcination method using tetrabutyl titanate as the titanium source and lignin as the carbon source. TiO₂ crystals with different morphologies could be successfully adsorbed onto the surface of biomass charcoal. These products were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG), derivative thermogravimetric (DTG), UV–vis diffuser flection spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FT-IR), and Brunauer–Emmett–Teller (BET). The photocatalytic activities of the as-obtained composites were checked under visible light irradiation. The results showed that both the microwave-hydrothermal temperature and time played an important role in the microstructure and photocatalytic activity of the samples. The rapid microwave-hydrothermal with the thermal post-treatment provides a promising route for the fabrication of biomass charcoal-doped nanocomposites materials.     

Tailoring the desired optical and mechanical performance of polyester‐plasticized PVC films: the role of different light stabilizers on the photo‐degradation

Effect of hindered amine light stabilizer (HALS: C944) and ultraviolet absorbers (UVAs: UV326, UV531) on the photo‐stabilities of polyester‐plasticized poly(vinyl chloride) (PVC) and polyester‐plasticized PVC/pigment yellow (PY) films were studied systematically. Both ultraviolet absorbers (UVAs) and hindered amine light stabilizer (HALS) could slow down the discoloration of polyester‐plasticized PVC and polyester‐plasticized PVC/PY films. However, the addition of UVAs protected polyester‐plasticized PVC films from being discolored and its efficiency is higher than HALS. The specific order of stabilizing effect on the photo‐oxidation is UV326 > UV531 > C944. For the optical performance, both UVAs and HALS could help to maintain the transmittance of visible light after photo‐degradation. The former could effectively adsorb ultraviolet (UV) light and resulted in lower transmittance of UV light. For the polyester‐plasticized PVC/PY systems, even though HALS and UVAs cannot help to maintain the shielding ability in high‐energy visible region after UV irradiation, they can help prevent the loss in transmittance of visible light. The surface morphology exhibited small holes on the surface of the films that contain UV531 or UV326; while large and deep holes were observed on the surface of PVC films without additives, C944‐doped and C944/PY‐doped films, indicating the higher UV‐stabilizing effect of UVAs. With regard to mechanical properties, UVAs and HALS can help to prevent the loss. Our present study systematically revealed the role of different stabilizers on the polyester‐plasticized PVC and polyester‐plasticized PVC/PY systems and paved the way to offer PVC materials with functional optical performance and desired long‐term performance using different light stabilizers. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis and Characterization of a New UV Cross‐linkable Waterborne Siloxane‐polyurethane Dispersion

A new cross‐linkable waterborne siloxane‐polyurethane dispersion (PEDA‐SiPU) was synthesized by incorporating the acrylate groups into the side chain of the polyurethane using the pentaerythritol diacrylate(PEDA) and introducing polysiloxane groups into the soft segment of the polyurethane using dihydroxybutyl‐terminated polydimethylsiloxane (PDMS). They can form the cross‐linking structure by UV radiation in the presence of a photo‐initiator. Fourier transform infrared spectroscopy (FTIR) was used to identify the chain structure of PEDA‐SiPU. The effect of the PDMS content and the PEDA content on the C?C conversion behaviors under UV irradiation was investigated. Water resistance and the mechanical properties of the UV cured films were also studied. Through the controlling of suitable content of PDMS and PEDA introduced in the chain, the obtained PEDA‐SiPU films were proved to possess both good water resistance and mechanical properties.